Color photographic silver halide emulsion containing a magenta colored cyan coupler



June 4, 1968 MAKOTO YOSH IDA ETAL 3,385,830

COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A MAGENTA COLOREDCYAN COUPLER 3 Sheets-Sheet 1 Filed Nov. 17, 1964 WAVE LENGTH 11,)

WAVELENGTH 560 WAVE LENGTH (mm m m Wm m A T S lf N 0 N W 0 W m, N w a IT KO W o U MMMW m June 1968 MAKOTO YOSHIDA ETAL 3,386,830

C(iLOR PHOTOGRAPHIC SILVER HALTDE EMULSION CONTAINING A MAGENTA COLOREDCYAN COUPLER Filed Nov. 1'7. 1964 5 Sheets-Sheet 2 (D Z 0.5- O [I O. O

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0 460 560 660 FIG. 5 WAVE LENGTH (m l) Lor t 0') Z a 0.5- O 0. O

460 560 660 Fl6.6 WAVE LENGTH (my) INVENTORS MAKOTO vosmaa KEISUKE 1084BY AKIO OKUMURA THEIR fiT/ORNG Y5 United States Patent 11 Claims.0196-100 ABSTRACT THE DISCLOSURE A color photographic silver halideemulsion containing a magenta-colored cyan coupler having a remarkableauto-masking action, represented by the following formula:

(in OR o ONH The present invention relates to color photographicmaterials containing colored cyan coupler, which is provided withautomatic masking mechanism, in order to remove drawbacks of colorreproduction of color sensitive materials.

Most of cyan couplers to be used for color photography arel-naphthol-Z-carboxylic acid derivatives or aminophenol derivatives.When these couplers are added in a photographic emulsion layer, thecoupler added must not diffuse to any adjacent photographic layers. Inorder to prevent diffusion from one photographic emulsion layer toanother, a long chain alkyl group and the like is introduced thereintoas a group for giving the couplers diffusion resisting property.Moreover, at least one carboxyl group I or sulfo group is introduced formaking the couplers soluble in aqueous alkali solution. Carboxyl group,however, is not sufiicient for this purpose, and therefore sulfo groupis used in general cases. In many cases, sulfo group is present at4-position of naphthol nucleus, or in aryl group or aliphatichydrocarbon group introduced in naphthol nucleons at 2-position or analiphatic hydrocarbon group combined with the said aryl group.

Cyan coupler substituted with arylazo group at 4-position is well knownas a coupler having automatic masking mechanism for correcting drawbacksof color reproduction of color sensitive materials. (Refer to U.S.Patents Nos.

"ice

2,449,966 and 2,455,169.) It is known that when1-hydroxy-4-arylazo-2-naphthoanilide type coupler substituted withhalogen, alkoxy group, or mono nuclear aryloxy group at ortho positionagainst amide group of anilide nucleus, which is represented by thefollowing general formula:

wherein X is halogen, alkoxy group, or mono nuclear aryloxy group; R ismono nuclear aryl group, is dissolved in a solvent such as tricresylphosphate and dispersed in an emulsion, absorption of green light isgreat and it is a coupler showing desirable color near magenta. (RefertoU.S. Patent No. 2,706,684.)

However, when the coupler represented by the abovementioned formula isdissolved or mixed in aqueous alkali solution, added into an emulsionand coated on the film base, the maximum value of absorption of thecoupler is present on the side of a short-wave length, as shown indotted lines in FIGS. 1,8, 5 and 7, absorption of blue light is great,that of green light is small, so quite unsatisfactory color is shown.That is to say, when this kind of coupler is dispersed in an emulsion byuse of an organic solvent, it shows excellent properties, but when it isadded in the emulsion by use of alkali, the properties thereof becomeamazingly inferior.

The accompanying drawing shows a spectral absorption curve of a couplerin a photographic film prepared from sensitive materials containing acoupler to be used in the present invention and a well known coupler forcomparison, and that of the coupler in a pyridine solution.

An object of the present invention is to provide sensitive materialscontaining 1-hydroxy-4-arylazo-2-naphthoanilide type coupler which haveexcellent properties, even when they are used by a process comprisingadding into an emulsion by use of alkali.

One reason why properties become inferior when this type of coupler isused by a process comprising adding into the emulsion by use of alkalimay be that the coupler is hardly soluble in aqueous alkali solution andcan not be dispersed well in the emulsion. Accordingly, in order to makethe coupler easily soluble in aqueous alkali solution and make it welldispersed in the emulsion, it is necessary to introduce carboxyl group,sulfo group and the like as solubilizing groups in coupler molecules.That is to say, ca-rboxyl groups, sulfo groups, or combination thereofshould be introduced in arylazo group at 4-position or anilide group atZ-position or both groups of naphthol nucleus. However, couplers havingcarboXyl group or sulfo group introduced into only arylazo group at4-position of naphthol nucleus are hardly soluble in aqueous alkalisolution as shown by Table 2. It is clear from the accompanying drawingthat when it is added in an emulsion together with alkali, theabsorption maximum of the coupler is present on the side of short wavelength, the absorption of blue light is great, the absorption of greenlight is small, and quite unsatisfactory color is shown.

Accordingly, in order to improve solubility of the coupler in aqueousalkali solution, to make dispersion of the coupler in the emulsionbetter, to produce excellent coupler showing quite suitable color nearmagenta, it is necessary to introduce carboxyl group or sulfo group intonot only arylazo group at 4-position but also anilide group at 2position of naphthol nucleus. In particular, it is desirable that sulfogroup giving better solubility than carboxyl group is introduced intoanilide group at 2- position. Moreover, as described later, carboxylgroup is not sufficient for making the color absorption better, and itis required that special effect on improvement of the color absorptionof sulfo group shall be well displayed. From this reason, sulfo group isbetter as the group introduced into anilide group at 2-position.Moreover, when this type of coupler is added into an emulsion and used,the diffusion of the coupler should be prevented. It is also necessaryfor preventing the diffusion of cyan dye resulting from the coupler bythe color development. Therefore, the diffusion-resisting group such aslong chain alkyl group should be introduced into anilide group at2-position of naphthol nucleus. That is to say, it is required thatthree substituents such as halogen or alkoxy group at the ortho positionagainst amido group, sulfo group and a diffusion-resisting group areintroduced into anilide group at 2-position of naphthol nucleus.Therefore, the synthesis of the parent coupler is extremely difiicultand expensive.

Accordingly, in case of the coupler in the present invention, alkoxygroup having more than carbon atoms is introduced into anilide group atortho-position against amido group, while sulfo group is introduced intoanilide group. Moreover, alkoxy group at ortho position against amidegroup is given properties of a diffusion-resisting group without losingspecial properties which affect color tone of the coupler. Therefore,merely two substituents are introduced into anilide group. The synthesisof the parent coupler is extremely easy, which is a characteristic fromthe point of synthesis. It may be said that the coupler to be used inthe present invention is a novel compound having a characteristic fromthe point of molecular structure, too.

That is to say, the present invention relates to color sensitivematerials, characterized containing the coupler represented by thefollowing general formula:

wherein R is alkyl group having more than 10 carbon atoms; M is a memberselected from the group consisting of a hydrogen atom, alkali metal,ammonium group, and H-NH (R") wherein p+q=3; p, q is 0-3; R" is loweralkyl group; Y is a member selected from the group consisting of --COOM,SO M, and carboalkoxy group; n is 1 or 2.

The coupler to be used in the present invention has not onlyalkali-solubilizing group in arylazo group at 4-position of naphtholnucleus, but also sulfo group in anilide group at 2-position, as shownby the above mentioned general formula. Therefore, said coupler is wellsoluble in alkali aqueous solution (refer to Table 2), and when it isdissolved in alkali solution and added in an emulsion, the coupler issatisfactorily dispersed. To our surpise, absorption of green light isgreat and suitable color almost similar to magenta is displayed.

When the coupler in the present invention and a coupler corresponding tothe general Formula I which is different from the general Formula IImerely in such point that SO M group is not present in anilide group aredissolved in pyridine, respectively, and their absorptions are measured.It is clear that they are almost same with each other in respect to theposition of the absorption maximum and shape of the absorption curve(refer to FIGS. 2, 4, 6 and 8). However, when said two couplers areadded in the emulsion by use of alkali, coated on a film base, dried,bleached and fixed, and spectral absorption of the resulting film aremeasured (refer to Example 1 and Example 2), remarkable differences areobserved between said two couplers (refer to FIGS. 1, 3, 5 and 7). Thatis to say, they are almost same with each other in pyridine solutions.However, when they are added into emulsions by use of alkali, thecoupler in the present invention which is represented by the generalFormula It has the absorption maximum at about 520 me and displays quitedesirable color, while the comparing coupler corresponding to thegeneral formula I which has not -SO M in anilide group has theabsorption maximum on the side of short wave length and displaysremarkably inferior color. The difference of their absorption maximumreaches from 25 to 50 m As being clear from these facts, it is animportant and essential condition that the coupler in the presentinvention has sulfo group in anilide group at 2-position of the naphtholnucleus.

Moreover, when the coupler in the present invention is added into ared-sensitive emulsion, coated on a film base, dried and exposed,developed with a color developer containing a developing agent such asN-N- disubstituted paraphenylenediamine, bleached and fixed, a negativecyan image developed and a positive red image of the residual coloredcoupler are obtained at the same time. The spectral absorption of theresulting positive image is quite desirable, as mentioned above, and thetransparency of the film is quite excellent. On the other hand, thecolor of the red image which is prepared by treating the comparingcoupler by the same treatment is inferior, and the conglomerate ofremaining coupler is observed in the film. Therefore, the transparencyof the film is inferior. As being clear from this fact, too, it is avery important condition for making dispersion of the coupler in theemulsion better, increasing the transparency of the resulting film andimproving the color of the red image that the coupler in the presentinvention has sulfo group in anilide group.

To our surprise, even in the case where carboxyl group introduced inarylazo group at 4-position of nap-hthol nucleus, as an alkalisolubilizing group, is subjected to este-rification and converted intocarboalkoxy group having lower alkali-soluble property, when the couplerhas sulfo group in anilide group like the coupler in the presentinvention, it is easily soluble in aqueous alkali solution and dispersedwell in the emulsion. The absorption maximum of the resulting filmreaches about 520 mp, quite desirable color is shown, and thetransparency of the film is good (refer to FIG. 9). The fact shows thatsulfo group present in anilide group can have alkalisoluble property tosufficient degree and disperses well in the emulsion, even though alkalis-olubilizing group is not included in arylazo group at 4-position ofthe naphthol nucleus. Moreover, the fact shows that the said sulfo grouphas special effect on making the color absorption better. Thecharacteristic that the coupler in the present invention has sulfo groupin anilide group is very important.

Furthermore, the coupler in the present invention is compared with thecomparing coupler having no sulfo group in anilide group with regard torelative speed of the cyan developed negative film prepared by theabovementi-oned treatment, as shown in the Tables 3 and 5. it clearlydepends on such structural characteristic as the coupler in the presentinvention has sulfo group in 5 6 anilide group, that the coupler in thepresent invention (X) 011 has a high speed. I

Couplers to be used in the present invention are repre- CONH sented bythe following formulae; i.e.

S03: (III) 0 H (I) 0181131 N C ONH- 10 (XI) 0 H 0 C1qHz5 H CONH C IS0311 C 0 01-1 (IV) OH 00151131 IfiI -0 ONH- (XII) O H O C1oH21 SOzH I 0ONE I 0 OH lfiI (v) on 00181131 N-O-ooon CONH The compounds of thepresent invention in form of free acid or salt have almost the sameeifect with each sloaH other.

The couplers in the present invention were prepared as N follows: Q O(1) (1-a).Triethylarnine salt of 3-amino-4-octadecyloxybenzene sulfonicacid (structural Formula e) (VI) (|)H (80121 1141 OH OH I -Q QNHQNHCOCH3 S oan (a) OOOH m n OC1s a1 N @NHCOCI-Ia G-Nlia COOH (b) (0)(vii) 11 00mm, (30mm 001m 0 ONH Q I SIOQH soar-r s BH-(OlHmN 000cm (d)(8) By acetylating 2-aminophenolwith acetic anhydride, 2- Lacetaminophenol (strucural Formula a) was obtained. The yield was 90%and the melting point was 2045 C. (IJOOCHa 2-acetaminophenol andoctadecyl bromide were dis- VIH OH 001 H7 solved in anhydrous alcoholand added with sodium ala 3 coholate. After refluxing, the formed sodiumbromide was filtered off, and poured into an aqueous hydrochloric acidsolution, whereby 2-octadecyloxyacetanilide (structural SOaH 0 Formulab) was separated. The resulting 2-octadecyloxyacetanilide was collected,added in a mixture solution con- 1 taining alcohol and an aqueouspotassium hydroxide solution, boiled, and refluxed. Thereafter, it wasadded in a concentrated aqueous hydrochloric acid solution, whereby 5hydrolysed products were precipitated in the form of hy- SiOBHdrochloride. The precipitates were filtered and treated 0H OCIBHW withan aqueous sodium hydroxide solution, and extracted I with ether, toyield Z-octadecycloxyaniline (structural O Formula 0) The yield Was 48%and the melting point was 57-58 C. 50311 2-octadecyloxyaniline wassulfonated by use of 30% fuming sulfuric acid according to a usualmethod, 3- amino-4-octadecyloxybenzene sulfonic acid (structural HFormula d) was obtained. The yield was 54% and the melting point was285-287 C.

220 g. of 3-amino-4-octadecyloxybenzene sulfonic acid was suspended in500 ml. of isopropanol, added with 60 g. of triethylamine, and boiledand refluxed on a steam bath for 30 minutes. After cooling, precipitateswere separated and filtered. The collected precipitates were washed with1000 ml. of acetone and dried to produce triethylamine salt of3-amino-4-octadecyloxybenzene sulfonic acid (structural Formula e). Theyield was 225 g. (83%) and the melting point was Ill-113 C.

(1b).-Triethylamine salt of l-hydroxy-Z-(2-octadecyloxy-5-sulfo)naphthoanilide (structural Formula 1) 65 g. of triethylaminesolt of 3-amino-4-octadecyloxybenzene sulfonic acid (The preparationmethod by using triethylamine salt is explained in the specification ofJapanese Patent No. 295,087) and 32 g. of 1-hydroxy-2-naphthoicphenylester were heated at 150 C. The formed phenol was distilled offunder a reduced pressure and, thereafter, cooled up to room temperature.Then, 150 ml. of acetone was added therein and heated. After theresulting solution was cooled, the separated precipitates werecollected, washed with 50 ml. of acetone, and recrystallized from 200ml. of methanol. 52 g. of triethylamine salt of1-hydroxy-2-(2-octadecyloxy-5-sulfo)nap hthoanilide was obtained. Theyield was 61%. The melting point was 129131 C. The content of thenitrogen was 3.81%

of observed value against 3.93% of calculated value.

(l-c).1-hydroxy-4-(3-carboxyphenylazo)-2 (2octadecyloxy-S-sulfo)naphthoanilide (structural Formula IV) 6 g. ofsodium hydroxide was added in 200 ml. of water, and 16.5 g. of 3-aminobenzoic acid was dissolved therein. Then, 9 g. of sodium nitrate wasadded to the resulting solution. Then, the solution was added with about50 g. of broken ice, cooled at 0 C., and added with 50 ml. of 36%hydrochloric acid under violent stirring.

On the other hand, 72 g. of triethyl amine salt ofl-hydroxy-2-(2-octadecyloxy-5-sulfo)naphthanilide was dissolved in 2000ml. of water together with 50 g. of sodium hydroxide, and cooled withice to about 7 C. Under stirring, a solution of diazonium salt preparedpreviously was dropped. After stirring, the mixture for about 1 'hour,150 ml. of 36% hydrochloric acid was added therein. Moreover, 1000 ml.of methanol was added and heated at about 50 C. Red precipitates sepa-rated were collected, washed with about 1000 ml. of water, and heatedand refluxed for about 30 minutes in 1000 ml. of methanol. Precipitateswere collected and dissolved in 250 ml. of dimethylformam-ide underheating. 300 ml. of methanol was added therein and cooled with water, toseparate precipitates. The precipitates were collected, washed with 500ml. of methanol, and dried, whereby 40 g. of 1hyd-roxy 4-(3carboxyphenylazo) 2 (2-octadecyloxy-5- sulfo)naphthoanilide wasobtained. The yield was 53% and the melting point was 275276 C.

(2) (2-a).-Sodiu.m salt of 1-hydroxy-2-(Z-octadecyloxy-5-sulfo)naphtho-anilide 61 g. of triethylamine salt prepared by the (1b)was dissolved in 250 ml. of hot methanol, and added with a solutioncontaining g. of anhydrous sodium acetate and 100 ml. of methanol. Theresulting solution was cooled with ice and the separated precipitateswere collected. The precipitates were washed with 30 ml. of methanol,and dried, to obtain sodium salt ofl-hydroxy-Z-(Z-ocetadecyloxy-S-sulfo)naphthoanilide. The yield was 32 g.(56%) and the melting point was more than 290 C.

( 2-b .1 hydroxy-4-( 3,S-dicarbomethyloxyphenylazo) 2 (2octadecyloxy-S-sulfo) naphthoanilide (structural Formula VII) Into 120ml. of water 25 ml. of 36% hydrochloric acid was added. Then, 126 g. of3,S-dicarbomethyloxyaniline was suspended therein, added with about 30'g. of broken ice. Under maintaining the temperature of the solutionbelow 5 C., 6 g. of sodium nitrite was dissolved in 30 ml. of water andthe resulting solution was dropped. On the other hand, 31.7 g. of sodiumsalt of l-hydroxy-Z- (2-octadecyloxy-5-sulfo)naphthoanilide was added in400 ml. of water together with 20 g. of sodium hydroxide, and heated atabout C. to dissolve. Thereafter, the solution was cooled to 5 C. Thesolution of diazonium salt previously prepared was dropped maintainingthe temperature of the solution below 8 C., while stirring. Then,stirring was carried out further for about 30 minutes. 40 ml. of 36%hydrochloric acid was added to the solution. Red precipitates separatedwere collected, washed with about 200 ml. of water, dried, boiled with amixture solution containing 50 ml. of dimethylformamide and 250 ml. ofmethanol, and washed with 250 ml. of methanol. After filtering at a hightemperature, the precipitates were washed with 100 ml. of methanol, anddried to yield 1 hydroxy 4 (3,S-dicarbomethyloxyphenylazo)-2-(2-octadecyloxy-S-sulfo)naphth-oanilide. The yield was 28.5 g. (69%) andthe melting point was 28l283 C.

(3).1 hydroxy 4 (2sulfophenylazo)-2-(octadecyloxy-5-sulf-o)naphthoanilide (structuralFormula VIII) In (1-c), 2-aminobenzenesulfonic acid was urged in placeof 3-amino benzoic acid. The sodium salt ofl-hydr-oxy-2-(2-octadecyloxy-5-su-lfo)naphthoanilide was used instead oftriethylamine salt of1-hydr0xy-2-(2-octadecyloxy-5-sulfo)naphthoanilide. By the sametreatment except using the above substances and recrystallized fromdimethylforrnamide l hydroxy-4-(2-sul fo henylazo) -2-(2-octadecyloxy-S-sulfo)n-a-phthoani-lide was obtained. The yield was andthe melting point was 290 C.

(4).1 hydroxy 4 (4 sulfophenylazo)-2-(2=dodecyloxy-S-sulfo)naphthoanilide (structural Formula X) In (l-a), triethylamine salt of3-amino-4-dodecyloxybenzene sulfonic acid was prepared by the sametreatment except dodecyl bromide was used instead of oct-adecylbromide.By the same treatment with (l-b), triethylamine salt ofl-hydroxy-Z-(2-dodecyl'oxy-5-sulfo) naphthoanilide was obtained, andtreated by the same manner as in (2-a) to prepare the sodium saltthereof. When the same treatment with (3) was carried out,1-hydrox'y-4-(4-sulfophenylazo)-2-(Z-dodecyloxy-S-sulfo)naphthoanilidewas prepared. The yield was 53% and the melting point was more than 290C.

With regard to concrete examples of couplers to be used in the presentinvention, the melting points and the results of nitrogen analysis areshown by the following table.

-c ONH C ONH- COOH COOH ( C iaHu The saturated excess amounts of thecouplers represented by the general formula of IV, IV, V, V, VI, VI, IXand IX respectively are measured, added in a sodium hydroxide solutionat pH 10 and stirred at 35.0 C. for o 6 days. The amount of the couplerremaining in the saturated solution is measured by spectroscopicanalysis. The solubilities are shown in Table 2 by molar ratio.

That is to say, it is clear that the coupler to be used in the presentinvention is more soluble in alkali than the comparative coupler.

Couplers represented by the structural formula of IV, IV, V, V', VI, VI,IX and IX, respectively are dissolved in a definite amount of pyridineand spectral absorption curve is measured. The maximum optical densityat visible region is adjusted at 1.0, and shown in the accompanyingdrawings, i.e. FIG. 2, FIG. 4, FIG. 6 and FIG. 8. That is to say, it isunderstood that the coupler to be used in the present invention isalmost same with the comparative coupler in pyridine solution in respectto the position of the absorption maximum value and shape of theabsorption curve.

EXAMPLE 1 Into 100 parts by weight of red sensitive silver iodobromideemulsion is added 5 parts by weight of a 5% sodium hydroxide aqueoussolution of the coupler prepared by the synthetic example (1-c);structural Formula IV, wherein 2.6 ml. of 1 N sodium hydroxide aqueoussolution per gram of the coupler is used. The pH value of the emulsionis adjusted at 7.0 by use of citric acid solution, coated on a filmbase, and dried to produce red-sensitive materials.

On the other hand, a saturated solution of a comparative couplerrepresented by the structural formula of IV, wherein 1 N sodiumhydroxide aqueous solution at C. is used, is prepared and added in partsby weight of red-sensitive silver iodobromide emulsion to be equivalentto the amount of the above-mentioned coupler represented by thestructural Formula IV. The pH value is adjusted at 7.0 by use of citricacid solution. By the same treatment with the above, red-sensitivematerials are produced.

The said two color sensitive materials are exposed to red light by lightWedge, and developed by a conventional method by use of the followingdeveloper con taining N-N-diethylparaaminoaniline.

Color developer: G. N-N-diethylparaaminoaniline sulfate 20 Sodiumsulfite 2.0 Sodium carbonate monohydrate 50.0 Hydroxylamine chloride 1.5Potassium bromide 1.0 Wate (makes up to 1000 ml.).

pH 10.8i0.1.

Moreover, the following bleaching solution and the fixing solution areused for bleaching and fixing. Undeveloped silver halide and reducedsilver formed are removed.

Bleaching solution: G. Sodium ferricyanide 100 Potassium bromide 20Water (makes up to 1000 ml. as a whole).

Fixing solution:

Sodium thiosulfate 200 Sodium sulfite 20 Acetic acid (2.8%) 45 Boricacid 7.5 Potassium alum 20 Water (makes up to 1000 ml.). pH 4.5:02.

A negative image developed in cyan and a red image consisted of residualcolored coupler are obtained at the same time from color sensitivematerials employing the coupler represented by the structural Formula1V. T ransparency of the film is very excellent. However, haze ofunreacted colored coupler are observed in the film produced from colorsensitive materials employing the comparative couple-r represented bythe structural Formula IV, and transparency of the film is inferior.

When the absorption maximum wave length of the film produced bybleaching and fixing said two kinds of color sensitive materials ismeasured, it is 520 mu in case of the coupler represented by thestructural Formula IV and 493 mg in case of the comparative coupledrepresented by the structural Formula IV. That is to say, in case of thecoupler represented by the structural Formula IV, this absorptionmaximum wave length in the film is long by about 27 mg, and quitedesirable color is shown (refer to FIG. 1).

The relative speeds of said two kinds of color sensitive materials areshown by the following table. The coupler to be used in the presentinvention is at high speed by about 10%.

The same treatment as in Example 1 is carried out, except that thecouplers corresponding to the structural Formulae P, VI and IX,respectievly, are used in place of the coupler corresponding to thestructural Formula IV, and that the comparative couplers represented bythe structural Formulae V, VI and IX, respectively, are employed insteadof the comparative coupler represented by the structural Formula IV,whereby each film is produced.

The film produced from the color sensitive materials employing thecoupler corresponding to the structural Formulae V, VI or IX, are quiteexcellent in respect to spectral absorption and transparency, as inExample 1.

On the other hand, when the couplers for comparison corresponding to thestructural Formula V, VI or IX is used, as in Example 1, haze ofunreacted color coupler is observed and Spectral absorption andtransparency of the produced film are inferior. Each of spectralabsorption curve of the film produced by bleaching and fixing theabove-mentioned color sensitive materials are illustrated in FIGS. 3, 5and 7, and the absorption maximum wave length is shown in the followingtable.

TABLE 4 Absorption maximum Structural formula: wave length (m V 525 V500 VI 520 VI 470 1X 515 IX 485 The relative speeds of color sensitivematerials produced are shown in Table 5.

What we claim is:

1. A color photographic silver halide emulsion containing the colorcoupler having the following general formula:

wherein R is alkyl group having more than 10 carbon atoms; M is a memberselected from the group consisting of a hydrogen atom, an alkali metal,an ammonium group and H-NH (R") wherein p+q=3; p, q are -3, and R" is alower alkyl group; Y is a member selected from the group consisting ofCO-OM, -SO M, and a carboalkoxy group; and n is 1 or 2.

2. The color photographic silver haide emulsion as claimed in claim 1,wherein said color coupler is 3. The color photographic silver halideemulsion as claimed in claim 1 wherein said color coupler is -0 ONE-COOH CONH

N=NOG 0 on 5. The color photographic silver halide emulsion as claimedin claim 1 wherein said color coupler is CONH SOsH

COOH N l OOH 6. The color photographic silver halide emulsion as claimedin claim 1 wherein said color coupler is CONH sour

000cm N I 7. The color photographic silver halide emulsion as CONH 0 Cism I SO 1];

13 14 8. The color photographic silver halide emulsion as OH claimed inclaim 1 wherein said color coupler is CONH- 5 SOaH CONH 10 11. The colorphotographic silver halide emulsion as rlOsmH claimed in claim 1 whereinsaid color coupler is CH CmHai 9. The color photographic silver halideemulsion as E claimed in claim 1 wherein said color coupler is 5 N CONHii 2() COOH References Cited E UNITED STATES PATENTS 25 2,688,539 9/1954Heimbach et a1. 96-100 2,979,405 4/1961 De Cat et al 96-56.6 10. Thecolor photographic silver halide emulsion as 3034892 5/1962 Gledhln et96-100 claimed in claim 1 wherein said color coupler is L TRAVIS BROWNPrimary Examiner

